Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

Patents

  1. Advanced Patent Search
Publication numberUS3355424 A
Publication typeGrant
Publication dateNov 28, 1967
Filing dateJul 29, 1964
Priority dateJul 29, 1964
Publication numberUS 3355424 A, US 3355424A, US-A-3355424, US3355424 A, US3355424A
InventorsBrown Lawrence H
Original AssigneeDow Corning
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Method for the preparation of aminoalkylsiloxane copolymers
US 3355424 A
Images(9)
Previous page
Next page
Description  (OCR text may contain errors)

United, States Patent 3,355,424 METHOD QR H R TIO F I H A KYLSILOXANE oPoLYMERs Law enc H B a n; Mid and M ch-,2 as s o D Corning Corporation, Midland, Mich., a corporation ofMichigan No Drawing. Filed July 29, 1964, Ser. No. 386,040

18 Claims. (Cl. 260-465) x is an integer of from to 2 inclusive, each R is an alkyl radical of less than 4 carbon atoms,

R is an aliphatic hydrocarbon radical containing a number of carbon atoms selected from the group consisting of 1, 3, 4 and 5 carbon atoms and having a valence of n+1, where n is an integer of from 1 to 3 inclusive,

is a monovalent radical attached to R by a carbonnitrogen bond and is composed of carbon, nitrogen and hydrogen atoms and contains at least 2 amine groups in which the nitrogen atoms are attached only to substituents selected from the group consisting of hydrogen, and aliphatic hydrocarbon, cycloaliphatic hydrocarbon, and aromatic hydrocarbon radicals, the nitrogen in Z being present only in said amine groups, the ratio of carbon atoms to nitrogen atoms in the substituent R'Z being less than 6:1, and each R is a monovalent hydrocarbon radical free of aliphatic unsaturation, and

(B) partial hydrolyzates formed by mixing (A) with up to 60 percent of its theoretical equivalent of water, with i (2) At least one organosiloxane of the average general formula where each R'" is selected irom the group consisting oi monovalent hydrocarbon radicals and halogenated monovalent hydrocarbon radicals, 4 i

m has a positive average value up to and including 2, y has an average value of from 1 to 2.5 inclusive, and the Sum of y+ni has an average value up to and including 3, the value of m being such'that the organo'siloxane (2) contains at least 1.0% by weight of hydroz yl groups, by contacting 1) and (2) liquid phase.

More particularly, the invention concerns the process which comprises reacting (1) At least one compound selected from the group i t n o (A) anes Q he o m l where x is an integer of irorn O to 2 inclusive, each R is a kyl d cal of e s ha 4 ca o a o s a ph i h drqc qa ica c nt i a numb r o srbtm 9 sslest t a he roup, c n stin of and m r han rbon at m a d. ha n a l n e o 3,355,424 Patented Nov. 28, 1967 where n is an integer of at least 1 Z is a monovalent radical attached to R by a carbomnitrogen bond and is composed of carbon, nitrogen and hydrogen atoms and c a n t l st 2 amine g u s t r tio o c on atoms t9 :n t ogs a m in the su s i n -L 'Zn being es than 6: 1, and each R" is a monovalent hydrocarbon radic l fr e o al p t c u sa r on a d (B) Partial .hydrolyzates formed by mixing (A) with up to :60 percent of its theoretical equivalent of water, with (2) At least one QrganQ iloxane of the average general formula I ice Wh re each R is sele ed o h group c s n o m no ale hyd oc rbon adic l nd hal enate monovalent hydrocarbon radicals, m has a positive average value up to and including 2, y has an average value of from 1 to 2.5 inclusive, and the sum of y+m has an ave g value p t and l d n y conta t g d in l qu p as i a mo n s ch tha e e is at least 10 percent by weight of 1) based on the combined weight of (1) and (2).

The salts of this invention are formed when the reaction product (I) of the above described process is reacted with (H) an acid, by contacting (l) and (II) in liquid P a e- The preparation of the (polyaminoalkyl)alkoxysilanes R" (Z ,R') Si(( )R) defined above is described in detail in the copending Speier applications Ser. Nos. 723,991 (filed Mar. 26, 8 and now issued as Patent No. 2,971,- 864) and 753,115 and 753,153 (both filed Aug. 4, 1958 and now abandoned after refiling as Ser. No. 176,797 on Mar. 1, 1962, the latter application also being now abandoned), all of which applications are assigned to the assignee of the present invention. The disclosures of the said copending applications are hereby incorporated by reference into the present application. In brief, these silanes can be produced by reacting a polyamine with a halogenohydrocarbonylalkoxysilane Where each halogen atom is on a carbon atom at least gamma to the silicon atom. Alternatively, they can be prepared by reacting the polyamine with an alpha-halogenohydrocarbonylalkoxysilane. In these reactions one nitrogen in the polyamine replaces a halogen atom in the halogenohydrocarbon radical, and the halogen acid is given off. The reaction is best carried out at temperatures of from 50 to 200 C. under anhydrous conditions using a molar excess of the polyamine.

The polyamines which can be employed include, for example, the following: ethylenediamine, diethylene-triamine, 1,6-heXanediarnine, 3-aminoethyl-1,6-diaminohexane, N,N'-dimethylhexamethylenediamine, cadaverine, piperazine, dl-1,2-propanediamine, methylhydrazine, 1- aminoguanidine, 2-pyrazoline, benzenetriamine, benzenepentamine, benzylhydrazine, N-methyl-p-phenylenediamine, N,N-dimethyl-p-phenylenediamine, and 3-o-tolylenediamine.

It can be readily seen that the polyamine employed can be an aliphatic, eycloaliphatic or aromatic hydrocarbon amine containing at leasttwo amine groups, one of which must contain at least one hydrogen atom. Thus the amine groups in Z are those in'which the nitrogen atoms are attached onlyto substituents selected from the group consisting of hydrogen, and aliphatic hydrocarbon, cycloaliphatic hydrocarbon, and aromatic hydrocarbon radicals, the nitrogen in Z-' being present only in said amine groups. The term poly in the specification is intended to include compounds or radicals containing two or more amine groups.

The halogenohydrocarbonylsilanes employed in the above described process can themselves be prepared by the well known addition reaction of a halogenated aliphatic hydrocarbon containing at least one unsaturated carbon to carbon linkage, with a halosilane such as that of the formula R",,SiHCl where R" and x are as previously defined, after which the addition product'is alkoxylated'by reacting it with one or more alcohols of the formula ROH. Platinum catalysts are preferred for the addition reaction and chloroplatinic acid is particularly suitable. Examples of suitable halogenated hydrocarbons include allylbromide, allyliodide, methallylchloride, propargylchloride, l-chloro-Z-methylbutene -2, S-bromopentadiene-l,3,16-bromo-2,6-dimethylhexadecene-2, and 'thelike. The halogenohydrocarbons can contain more than one halogen atom, as in 3,4-dibromobutene-1 and 3- chloro-2-chloromethylpropene-1, so that the radicals resulting therefrom can react with more than one amino nitrogen atom, i.e. n can be greater than 1. Preferably there should be no more than one halogen atom per carbon atom. Furthermore, no halogen atom can be so positioned that after the addition of the halogenohydrm' carbon to the silicon there is a halogen atom on a carbon atom which is beta to the silicon.

A second method for preparing the halogenohydrocarbonylsilanes described above is that of halogenating an alkylhalosilane with elemental halogen followed by reaction with an alcohol to give the halohydrocarbonylalkoxysilane. This is the method employed when R in the above formula is a methylene radical.

In the (polyaminoalkyl)alkoxysilane reactants, R' can be any aliphatic hydrocarbon radical containing 1 or more than 2 carbon atoms and having a valence of at least two, i.e. it can include, in any aliphatic configuration,

any combination and any number of methyl, vinyl,

methylene, vinylene,

I I -CH--, and (i,-

prises primary amine, secondary amine (including imine) and tertiary amine groups.

The radical (RZ can be of any length, so long as I the ratio of carbon to nitrogen in the radical is less than 6,1. As a practical matter, the R' radicals will ordinarily contain no more than 18 carbon atoms, and preferably contain 1 or 3 to 5 inclusive carbon atoms. The preferred Z radicals contain from '1 to 8 carbon atoms, and n is preferably 1, 2, or 3.

R" can be any monovalent hydrocarbon radical free of aliphatic unsaturation. Preferably, however, it contains a maximum of 18 carbon atoms. Illustrative examples of cals such as phenyl, xenyl, and naphthyl; alkaryl radicals such as tolyl and xylyl; aralkyl radicals such as benzyl; and cycloaliphatic radicals such as cyclohexyl, methyl, ethyl, and phenyl are most preferred.

The R radicals can be any alkyl radical of less than 4 carbon atoms, i.e., methyl, ethyl, propyl, or isopropyl radicals. Each R, R, R, or Z radical in the above silane reactant can of course be the same as or different from each of its fellow radicals in a single reactant or in a mixture of reactants of a single type, as the case may be.

The partial hydrolyzates (B) defined above are readily prepared by merely mixing the silane (A) with water. The water is used in any amount up to 60 percent of the theoretical equivalent. The theoretical equivalen of water is that minimum amount which theoretically would b'ringabout the complete hydrolysis of all of the siliconbonded alkoxy groups, calculated as though hydrolysis is followed by complete condensation to siloxane linkages. In other words, 1 mol of water is equivalent to 2 mols of alkoxy, as illustrated by the simplified equation:

The hydroxylated organosiloxanes (2) employed as the second reactant herein are a well known type of compound. As noted previously, they can be defined as having the average general formula icals such as vinyl, allyl, cyclohexenyl, and propynyl;

and halogenated radicals such as bromophenyl, tetrachlorophenyl, chloroxenyl, u,u,a-trifluorotolyl, 1,1,1-trifluoropropyl, and the like. The preferred radicals are methyl, phenyl, and vinyl. Each R'" radical can be the same as or different from its fellow R' radicals.

The requirement that y in the above formula should have an average value of from 1 to 2.5 does not preclude the presence of some silicon atoms in reactant (2) which have either 0 or 3 R radicals attached thereto. In other words, the reactant can be defined as an organosiloxane which consists essentially of polymeric units of the formula R,Si(OH) O and in such a definition it is obvious that y can be an integer of from 0 to 3 inclusive in any one unit, so long as the average value is from 1 to 2.5 in the polymeric organosiloxane. Preferably the maximum average value for y is 2.1. It is also obvious that in any given unit, m can be 0 so long as it has a positive value in some other unit or units in the polymer. Since there must be siloxane linkages in this polymeric reactant, the sum of y+m in any given unit cannot be more than 3. Preferably the sum of y+m in any particular unit will be from 1 to 3 inclusive, and the average value of this sum in the polymer will necessarily range from greater than 1 up to and including 3. It is most preferred that m does not exceed a value of 1 either in a particular unit or as an average value for the polymer, and that the average value be such that the reactant (2) contains at least 1.0 percent by weight of the silicon-bonded hydroxy groups, with best results being obtained at about 1.8 to 6.0 percent inclusive hydroxy groups. I

As is well known in the art, the organosiloxane reactants (2) defined above can be prepared by the hydrolysis or cohydrolysis of the corresponding organohalosilanes or organoalkoxysilanes under conditions such that the condensation of the resulting silanols does not proceed to completion. This technique is preferred where the degree of substitution (i.e. the average value of y)-is less established, then washing the product with water until it is free of acid. The amount of hydroxy groups in the final product is controlled by the concentration of the acid. This technique is set forth in detail in US. Patent No. 2,779,776, issued Ian. 29, 1957. Other suitable methods are also known to the art, as, for example, in US. Patent- No. 2,863,897, issued Dec. 9, 1958 and No. 2,607,792, issued Aug. 19, 1952.

Where the hydroxylated organosiloxane reactant (2) has a degree of substitution (d.s.) less than about 1.9, the reactants and products obtained by this invention are essentially resin-forming in nature. Above a d.s. of 1.9, the reactants and products tend to be fluid in nature. One type of preferred organosiloxane reactant (2) can be defined as consisting essentially of polymeric units of the formula where Me, Ph and Vi represent methyl, phenyl and vinyl radicals respectively, a is an integer of from O to 3 inclusive, b is an integer of from 0 to 2 inclusive, 0 is an integer of from 0 to 1 inclusive, the sum of a+b+c is from 1 to 3 inclusive and has an average value of from 1 to 2.5 inclusive, m is an integer of from 0 to 2 inclusive and has an average value such that (2) contains at least 1 percent by weight hydroxy groups, and the sum of a+b+c+m is an integer of from 1 to 3 inclusive. A particularly preferred specie is a hydroxy end-blocked dimethylpolysiloxane having at least 1.0 percent by weight silicon-bonded hydroxy groups, and preferably from 1.8 to 4.0 percent of such groups.

The reaction of this invention takes place by merely contacting the reactants (1) and (2) in liquid phase. Often it will proceed rather slowly at room temperature, however, so it is preferred to expedite the matter by heating the reaction mixture at, forexample, 50 to 200 C., with best results in the range of 65 to 150 C. Heating also tends to drive the reaction toward completion, i.e. toward the formation of the maximum number of new siloxane linkages, particularly when the by-produced alcohol is removed. The reaction, in simplified form, is illustrated by the following equation EsioR+HosiE+ ESlOSlE-I-ROH The reaction appears to be self-catalyzed by the polyaminoalkyl substituents present in reactant (1). These substituents also catalyze the condensation of siliconbonded hydroxy groups, however, so when the dis. of the system is in the resin-forming area (i.e., below about 1.9) it is preferred that the reaction and the reaction product be kept in an inert solvent to prevent or retard gelation. Any inert organic solvent (e.g. hydrocarbons such as benzene, toluene, xylene, mineral spirits, etc.) can be used, but it is preferred that water soluble organic solvents be employed. Examples are the various Well known water soluble ethers (e.g., dioxane), ketones (e.g. acetone), esters (methylcellosolve acetate, methyl acetate, ethylene glycol diacetate), and alcohols (methanol, ethanol, 2-propanol).

The alcohol which is formed in this reaction can be removed by distillation, thus it is certain that true copolymers are formed. It will be readily apparent that the copolymer can have unreacted (OR) and/or (OH) groups present, depending upon the relative amounts of the two reactants and the amount of (OR) or (OH) present in the reactants initially. If desired, any excess (OR) groups present can be hydrolyzed by the addition of water to the system, and control of the amount of water so added controls the amount of such groups which remain in the copolymer. Preferred products are obtained when water hydrolysis can be left in the reaction product, if desired. In aqueous and/or alcoholic solutions or dispersions, the copolymer actually is in a state of equilibrium, and determination of the precise amounts of silicon-bonded (OH) or (OR) present is ordinarily not feasible.

The reactants are employed in an amount such that there is at least 0.001 percent by weight, and preferably at least 1%, of the polyaminoalkyl-substituted reactant (1) based on the combined weight of '(l) and (2 Any excess of (1) can be used. However, most preferably the weight ratio of 1) to (2) will line in the range of from 1:9 to 9:1, and the most interesting products have been obtained where the ratio ranges from 2i 8 to 8:2. Since reactant (1) can contain varying amounts of nitrogen, depending upon its exact structure, obviously the amount of nitrogen in the copolymeric product can vary accordingly for differing (1) reactants. As noted above, it is most preferable that at least 10 percent by weight of (1) be used, but in addition to this it is preferred that the amount of (1) be adjusted according to its particular structure so that the resulting copolymer contains at least 1.8 percent nitrogen by Weight.

It will be seen that a number of variations of the basic reaction are possible, considering that solvent may or may not be present, that added water may or may not be used, that if Water is used it can be added at different stages in the process, and that the hydroxylated siloxane reactant 2) can be formed in situ by using, for example, an alkoxysilane and water. The choice of the best process will vary with the type and relative amounts of reactants as well as with the extent of hydroylsis and/or condensation desired in the final product. Examples of important variations are as follows, where for simplicity the polyaminoalkyl-substituted reactant and the hydroxyl ated organosiloxane reactant are referred to as 1) and (2) respectively:

A. Mixture of (1), (2), and solvent is made. Water is then added and mixture is heated at reflux. Used for solid 2) at high content of (1).

B. Mixture of (1), (2), and solvent is heated at reflux. Used for solid (2), usually at lower (1) content. Gives greater shelf stability, lower viscosity than A.

C. Mixture of (l), (2), and solvent s heated at reflux,

then water and optional additional solvent are added and reflux continued. Optional process for A, gives better water solubility.

D Mixture of (l) and (2) is heated, then water and solvent added and mixture refluxed, optionally stripping out formed alcohol and solvent. Used with (2) which is a fluid or high d.s. resin.

E. Mixture of (1) and (2) is heated, cooled, and op- .tional solvent added. Used where (2) is fluid. Alterna- .hydrobromic, nitric, sulfuric, and carbonic acids. Any

organic acid can be used, but it is preferred to employ those which have no more than 8 total carbon atoms and which have a ratio of no more than 5 (preferably no more than 4 ,noncarboxylic carbon atoms for each carboxylic carbon atom. The acids can be monocarboxylic, as in formic, acetic, propanoic, butyric (i.e. butanoic), valeric (peutanoic), and caproic (hexanoic) acids, including branched chain acids such as pivalic (trimethylacetic); or polycarboxylic as in oxalic, malonic, succinic, glutaric, adipic and pimelic acids. Hydroxy aidsare also suitable, as exemplified by latic, malic (hydroxylsuccinic) and tartaric acids. Citric acid is a suitable hydroxylated tricarboxylic acid. Aromaticssuch as phthalic, isophthalic, and terephthalicacids .can be used. Unsaturated acids also can be used, maleic acid being a preferred example. Halogenated acids such as trichloroand trifluoroacetic are also suitable. Any other substituent groups can be present in the acid, but it is preferable that the carboxylic groups are the only groups present which are reactive toward the amino-substituents present in the organosiloxane.

One of the major reasons for preparing salts of the defined copolymeric reaction products lies in the fact that the salt form is ordinarily more water soluble than its parent compound. To enhance this effect, it is preferred to prepare the salt from an acid which is itself water soluble to an appreciable extent. However, even acids which are only very slightly soluble (such as caproic) produce salts which are more soluble than the starting organosiloxane. The salts tend to have a greater stability in storage (i.e., shelf life) than their parent compounds, and are also useful in any situation where the alkalinity of the original amine groups is undesirable.

The amount of acid employed will ordinarily be that which just neutralizes the aminoalkyl-substituted organosiloxane. In other words, ordinarily the acid will be used in an amount to provide about one equivalent of acid for each amine nitrogen atom present in the organosiloxane. Of course any amount less than this can be used, if desired, to provide a partial salt having solubility characteristics intermediate between the organosiloxane per se and the full salt. Such a partial salt is meant to be included within the scope of the term acid salt as it is employed herein. An excess of acid over the equivalent amount can also be used, subject only to the practical limitation imposed by any harm which a large excess of acid might do to any system in which the salt is to be used.

The copolymers and salts prepared in accordance with this invention are generally water-miscible materials. The term water-miscible" is used herein as inclusive of both water soluble and self-emulsifiable materials. In general, the salts defined herein are truly Water soluble in the usual sense of that term. The same is also true of those copolymers which are not salts but which contain a sufficient amount of the polyaminoalkyl-substituted polymeric units to impart Water solubility. In a dimethylsiloxane copolymer salt system, for example, those copolymers which contain at least 20 to 25 percent by weight of the polyaminoalkyl-substituted units will generally be truly water soluble. Copolymer salts containing a lesser amount of polyaminoalkyl-substituted units, e.g. 10 to 20 percent in the aforesaid dimethylsiloxane copolymer system, are generally self-emulsifiable. By this it is meant that the latter copolymers do not form true solutions, but do form stable emulsions with water even in the absence of any added emulsifying agent, i.e., no third ingredient is necessary to form an emuslion.

In the absence of any inert solvent, some of the fluid copolymers of this invention tend to gel in a matter. of hours or days. This effect can be retarded either by storing the copolymer in solution in a solvent such as an alcohol, or by converting the copolymer to a salt. Even the alcoholic solutions of the salt forms of these copolymers may gel in a matter of months, however, and the most stable and hence preferred form for storage is as a solution of the salt in the alcohol (or other watersoluble solvent).

One major utility of the copolymers and salts of this invention is as sizing agents on textile materials, including glass fiber products. A prime coating of these products improves the ease and degree of coloring obtainable from the application of dyes or pigments to fabrics which are otherwise difficult or impossible to color. Such uses are described in detail in the copending application of John L, Speier filed concurrently herewith and entitled Process for Dyeing Textile Fibers (Ser. No. 28,851). The products of this invention are also useful as emulsifying agents for conventional organosiloxane fluids. Those products having a degree of substitution in the lower ranges (e.g., 1 to 1.9) are resinous or resin-forming in nature, and can be used as coating, impregnating, or laminating resins and the like, in the same manner as the well known commercial silicone resins. The presence of the polyaminoalkyl substituents in such resins makes them easier to cure, and in fact renders many of the airdrying so they will cure at room temperature.

In the following examples, which are illustrative only, all parts and percentages are by weight unless otherwise specified, The symbols Me, Et, Pr, Vi, and Ph have been used to represent methyl, ethyl, propyl, vinyl, and phenyl radicals respectively.

Example 1 A mixture was prepared containing 75 g.

( MeO) Si (CH NHCH CH NH and 25 g. of a polymer having the formula (HO Me SiO (Me SiO ,SiMe (OH) where the average value of a was such that the polymer contained 3.5 percent by weight of (OH) groups. Such a mixture contains about 1.01 mols (OMe) groups and 0.05 mol (OH) groups. The mixture was heated to 150 C. under a reflux condenser, cooled, then 8.65 g. H O (0.48 mol, equivalent to the 0.96 molar difference be tween the OMe and OH groups) was added, followed by 75 g. EtOI-I (sufficient to provide a solution of about 50 percent of the theoretical organosiloxane product). About one third of the alcohol was removed by distillation and then the product was readjusted to a 50 percent concentration. The resulting ethanol solution was com-.

pletely soluble in water, and the copolymer product present therein contained about 75 percent.

NHioHioHrNH(oHmsuoMe) .o T

units and 25 percent Me SiO units by weight. The value of z in this copolymeric solution could not be measured because of the alcohol present as solvent, but theoretically would range between 0 and 1. When the alcoholic solution of such a copolymer is itself dissolved in water, a

major portion of any residual silicon-bonded methoxy groups are hydrolyzed. When such an aqueous solution is dried, hydrolysis and condensation of the copolymer become substantially complete so that the copolymer then consists essentially of only Me SiO and NH CH CH NH CH SiO units. An aqueous solution containing 1 percent of the coplymer was applied to a glass fiber textile. The textile was dried 20 minutes at 225 F., and it was then possible to color it with various pigments or dyes, using conventional techniques. Acid dyes were found to give best results. Color was retained by the glass even after laundermg.

A salt of a copolymer prepared exactly as above was prepared by adding 40.5 g. glacial acetic acid (0.676 mol) to the cool 50 percent alcohol solution, thus providing 1 mol of acid for each gram atom of nitrogen present in the copolymer. The alcoholic solution of the salt was completely soluble in water. Treatment of glass fiber textiles with aqueous solutions of the salt made it possible to dye them in the same manner as described above, where the original copolymer was used.

Copolymers and salts similar to those specifically illustrated above were made from the same reactants by the same technique, but using ratios of 10/90, 25/75, 50/50, and /10 in place of the 75/25 ratio described above. Related 50/50 copolymers were prepared by the same technique, except that MeO MeSi CH NHCH OH NH 1 MeO MeSiCH CHMeCH NHCH CH NH -01 9 (MeO) Si(CH NHCH CH N (CH CH CN) 2 were used in place of the MeO Si (H NHCH Cl-l NH reactant.

Example 2 A mixture was prepared of 362 g.

(MeO) Si CH NHCH CH NH and 1085 g. of a fluid polymer having the formula (HO) Me SiO (Me SiO SiMe (OH) where a had an average value such that the polymer contained 3.09 percent (OH) groups. The latter type ,of polymer is lcnown as a hydroxy end-blocked dimethylpolysiloxane, and this mixture represented a 25/75 ratio of aminosilane to polymer. The mixture was agitated intermittently for 3 hours, during which time the exothermic reaction which took place raised its temperature from the initial 24 C. to a final 31 C. The reaction product was diluted with 550 g. isopropanol, and to the resulting solution there was added a solution of 203 g. glacial acetic acid in 1100 g. isopropanol (representing a stoichiometric amount of acid and sufiicient alcohol to provide about a 50 percent concentration of nonvolatiles). The alcoholic solution of this salt was soluble in water, and application of the aqueous solution to glass cloth made it possible to dye the glass as in Example 1.

When the above process is repeated except that equivalent amounts of hydrochloric, hydrobromic, nitric, sulfuric, formic, propanoic, malic, adipic, trifluoroacetic, or isophthalic acids are used in place of the acetic acid, comparable salts are produced.

Example 3 A mixture was made of 500 g.

(MeO) Si(CI-I NHCH CH NH and 1500 g. of the hydroxy end-blocked dimethylpolysiloxane containing 3.09 percent (OH) groups. The temperature rose from 27 C. to 35 C. in 3 minutes from the exothermic reaction. The mixture was heated up to 152 C. over a period of 105 minutes, during which time 83.5 g. of the by-product MeOH was removed. The resulting viscous mass was cooled to 50 C. and diluted with 800 g. ethanol, then 270 g. glacial acetic acid in about 1,000 g. EtOH was added. The alcoholic solution of the salt so produced was water soluble, and acted as a mordant for dyeing glass cloth in the same manner as the products of Examples 1 and 2.

Example 4 When a mixture of 190 g.

MB2(MEO) NHCH CH NH and 556 g. of a hydroxy end-blocked dimethylpolysiloxane containing 3.06 percent (OH) groups is reacted as in Example 3, diluted to 50 percent solids with ethanol, and converted to a salt by the addition of 120 g. glacial acetic acid, a water soluble product is obtained.

Example 5 A partial hydrolyzate of (MeO) Si(CH NHCI-I CIrI NI-I was prepared by mixing 92 g. of this amine with 4.5 g. water (about 40 percent of the theoretical amount for complete hydrolysis). When this partial hydrolyzate is reacted with 23.0 g. of the dimethylpolysiloxane of Example 3 by the method of that example, diluted to 50 percent solids with ethanol, and converted to the salt 'by the addition of 50 g. glacial acetic acid, the solution of product is water soluble.

10 Example 6 and mol percent Me SiO units (both copolymers containing about 3 percent (OH) groups) are used in place of the dimethylpolysiloxane, the resulting alcoholic solutions of the acetate salt are water soluble.

Example 7 An organosiloxane hydrolyzate having a high hydroxy content and a d.s. of 1 was prepared by adding a mixture of 70 mol percent PhSiCl and 30 mol percent PrSiCl to a stirred mixture of ice water (sufficient to provide a theoretical 15 percent HCl concentration upon completion of the hydrolysis), methanol (3 mols per mol of silane), and toluene (sufiicient to provide 30 percent silicone solids in final toluene solution). The organic layer was separated, washed, and volatiles stripped off to a temperature of C. The residue was stirred With additional water (5 percent of the Weight of the starting chlorosilanes), and then all solvent was removed by distillation to a pot temperature of C. at 20 mm. Hg pressure. The product was a solid resin, and contained 6 percent siliconbonded hydroxy groups.

Heat and agitation were applied to a mixture of 1200 g. of the above solid resin and 1200 g. ethanol until the resin dissolved. To this solution there was added 400 g. (MeO) Si(CI-l NHCH CH NH causing an exothermic rise in temperature from the starting 39 C. to a final 44 C. The resulting solution was heated at reflux (about 76 C.) for 3 hours, then cooled and diluted to about 45.5 percent solids by the addition of 400 g. ethanol. This reaction product was found to be compatible with alcoholsoluble phenolic laminating varnishes, thus providing a convenient means for the silicone modification of such varnishes. (In general, commercial silicone resins are not compatible with these phenolics.) The reaction product was also compatible with conventional organosiloxane coating resins, and was found to have a catalytic effect on the curing thereof. For example, one conventional resin (containing about 55 mol percent PhMeSiO, 30 mol percent MeSiO and 15 mol percent PhSiO units) ordinarily requires about 4 hours at 250 C. for curing and cannot be cured at room temperature, but when 90 parts of this resin was blended with 10 parts ofthe above reaction product (the ratio being on a resin solids basis), the mixture was found to cure in about 24 hours at room temperature.

Another organosiloxane hydrolyzate was prepared by the technique used in making the hydrolyzate of Example 7, but the mixture of silanes used for hydrolysis was composed of 20 mol percent'PhMeSiCl 30 molpercent MeSiCl 40 mol percent PhSlClg, and 10 mol percent Ph SiCl The solvent-free hydrolyzate was a viscous liquid containing about 2.5 percent (OH) groups. A solution of 300 g. of this hydrolyzate in 300 g. EtOH was mixed with 100 g. (MeO) Si(CH )3NHCH CH NI-I producing a rise in temperature from.22" :C. .to 30 C. 11112 minutes. A solution of 14 g. H O in 25 g. EtOH was added Example 9 When the process of Example 8 is repeated except that the hydrolyzate is prepared from a mixture of 20 mol percent PhMeSiCl 25 mol percent MeSiCl 5 mol percent ViSiCl 40 mol percent PhSiCl 9 mol percent Ph SiCl and 1 mol percent Me SiCl, a comparable water soluble product is obtained.

Example 10 A mixture of 45 mol percent Me siCl 30 mol percent Ph SiCl and 25 mol percent PhSiCl was added to a stirred hydrolysis mixture containing methylisobutylcarbinol (0.25 mol per mol silane), toluene (to provide 30 percent solids of theoretical silicone in final toluene solution), and water (sufficient to provide theoretical percent HCl solution). The hydrolyz ate was washed and solvent removed by distillation to provide a solvent-free liquid product having a viscosity of 9400 cs. at 25C. and containing 3.75 percent (OH) groups. A mixture of 70 parts of this hydrolyzate and 30 parts of (MeO) Si (CH NHCH CH NH was heated to about 100 C., then cooled, diluted with 100 parts EtOH and 2 parts H 0, and heated at reflux temperature for 3 hours. The reaction product was then cooled and a salt was formed by 'adding 16.2 parts glacial acetic acid. The salt solution Waswater soluble.

Example 11 When (EtO)gEtSi(CHz)3NHCHzCH2NH2 (E130)2PhSi(CH2)aNHCH2CHrNHz (MeO)aSiCH2C HzCHNH CHQCHzNHz, (MeohsiCHzNHCfiHiNMeg is substituted for the (MeO) Si(CH NHCH CH NH used in the preparation of the copolymers shown in Example 1, using an equivalent molar amount in each case, the resulting copolymers and salts are comparable in their properties to those obtained in Example 1.

Example 12 A mixture of 1776 g. of a hydroxy end-blocked dimethylpolysiloxane containing about 4 percent hydroxyl groups and 134 g. of (CH O) Si(CI-I NHCH CH NH was prepared and allowed to stand for 3 hours with intermittent shaking. Then a mixture of 75.4 g. of glacial acetic acid and 269 g. of isopropanol was added to the above mixture and mixed in by shaking. The resulting mixture was then allowed to stand for one-half hour with shaking every 5-10 minutes. Then 1000 g. of isopropyl alcohol was added.

The resulting product was essentially an isopropanol solution of the acetate salt of a copolymer consisting of units and units.

Example 13 When a mixture of a hydrolyzate formed by mixing 50 percent of the theoretical equivalent of water with 10 g. of H NCH CH NHCH CH(CH )CH SKOCH and 190 g. of a hydroxyl endblocked dirnethylpolysiloxane containing about 4% hydroxyl groups is heated in liquid phase at a temperature of about 100 C., a copolymer consisting of NH CH CH NHCH CH(CH )CH SiO units and (CH SiO units is obtained.

12 Example 14 When 2 g. Of and 198 g. of the hydroxyl endblocked dimethylpolysiloxane are substituted for the materials of Example 13, a copolymer consisting of H NCH CH NH(CH SiO units and (CH SiO units is obtained.

That which is claimed is:

1. A process for the preparation of polyaminoalkylsubstituted organosiloxane copolymers which comprises reacting (1) At least one compound selected from the group consisting of (A) silanes of the formula R" (Z R')Si(OR) Where:

x is an integer of from 0 to 2 inclusive, each R is an alkyl radical of less than 4 carbon atoms,

R is an aliphatic hydrocarbon radical containing a number of carbon atoms selected from the group consisting of 1, 3, 4 and 5 carbon atoms and having a valence of n+1, where n is an integer of from 1 to 3 inclusive, is a monovalent radical attached to R b a carbon-nitrogen bond and is composed carbon, nitrogen and hydrogen atoms and contains at least 2 amine groups in which the nitrogen atoms are attached only to substituents selected from the group consisting of hydrogen, and aliphatic hydro carbon, cycloaliphatic hydrocarbon, and aromatic hydrocarbon radicals, the nitro gen in Z being present only in said amine groups, the ratio of carbon atoms to nitrogen atoms in the substituent -RZ being less than 6:1, and each R" is a monovalent hydrocarbon radical free of aliphatic unsaturation, and

(B) partial hydrolyzates formed by mixing (A) with up to percent of its theoretical equivalent of water, with (2) At least one organosiloxane of the average general where each R'" is selected from the group consisting of monovalent hydrocarbon radicals, and halogenated monovalent hydrocarbon radicals,

m has a positive average value up to and including 2,

y has an average value of from 1 to 2.5 inclusive, and the sum of y-I-m has an average value up to and including 3, the value of m being such that the organosiloxane (2) contains at least 1.0% by weight of hydroxyl groups,

by contacting (l) and (2) in liquid phase in an amount such that there is at least 10 percent by weight of (1) based on the combined weight of (l) and (2).

2. A process in accordance with claim 1 further charac terized in that the copolymeric reaction product (I) of the process of claim 1 is reacted with (11) an acid selected from the group consisting of hydrochloric, hydrobromic, nitric, sulfuric, and carbonic acids and organic acids having a ratio of no more than 5 noncarboxylic carbon atoms for each carboxylic carbon atom, by contacting (I) and (II) in liquid phase, whereby the corresponding acid salt is produced.

3. A process for the preparation of polyaminoalkylsubstituted organosiloxane copolymers which comprises reacting (1) a compound of the formula n snornmo where each R'" is selected from the group consisting of monovalent hydrocarbon radicals and halogenated monova'leut hydrocarbon radicals,

y has an average value of from 1 to 2.5 incluslve,

m has a positive average value up to and including 2, and the sum of y+m has an average value up to and including 3, the value of in being such that the organosiloxane (2) contains at least 1.0% by weight of hydroxyl groups,

by contacting (1) and (2) in liquid phase in an amount such that there is at least 10 percent by weight of (1) based on the combined Weight of (1) and (2), and such that there is an excess of (OR) groups in (1) over the (OH) groups in (2); adding an amount of water which is at least equivalent to the molar difierence between the OH groups present in (2) and the OR groups present in (l), and heating the mixture at a temperature of at least 65 C.

4. A process in accordance with claim 3 further characterized in that the copolymeric reaction product (I) of the process of claim 3 is reacted with (II) a water soluble acid selected from the group consisting of (A) inorganic acids from the group hydrochloric, hydrobromic, nitric, sulfuric, and carbonic acids, and (B) organic acids having a ratio of no more than 5 noncarboxylic'carbon atoms for each carboxylic carbon atom, by contacting (I) and (II) in liquid phase;

5. A process for the preparation of polyaminoalkylsubstituted organosiloxane copolymers which comprises reacting (1) the hydrolyzate formed by mixing up to 60 percent of the theoretical equivalent of water wtih a compound of the formula where each R is an alkyl radical of less than 4 carbon atoms, with (2) an organosiloxane consisting essentially of polymeric units of the formula R' Si(OH) O where m is an integer of from 0 to 2 inclusive and has an average value such that (2) contains at least 1.0 percent by weight hydroxy groups,

y is an integer of from 0 to 3 inclusive and has an average value of from 1.0 to 2.5 inclusive, the sum of y+m being from 1 to 3 inclusive, and each R' is selected from the group consisting of monoval'ent hydrocarbon radicals and halogenated monovalent hydrocarbon radicals,

by mixing (1) and (2) and heating the mixture in liquid phase at a temperature of at least 65 C., the proportions of (1) and (2) being such that there is at least percent by weight of (1) based on the combined weight of 1) and (2).

6. A process for the preparation of polyaminoalkylsubstituted organosiloxane copolymers which comprises reacting (1) a compound of the formula 14 where each R is an alkyl radical of less than 4 carbon atoms, with (2) a hydroxy end-blocked dimethylpolysiloxane having from 1.0 to 6 percent by weight silicon-bonded hydroxy groups, the weight ratio of (1) and (2) being' from 1:9 to 9:1, by mixing (.1) and (2) and heating the mixture in liquid phase to at least 65 C.

7. A process for the preparation of polyaminoalkylsubstituted organosiloxane copolymers which comprises mixing, in liquid phase,

(1) a compound of the formula where each R is an alkyl radical of less than 4 carbon atoms, with (2) a hydroxy end-blocked dimethylpolysiloxane having from 1.0 to 6 percent by weight silicon-bonded hydroxy groups, in a ratio such that there is an excess of (OR) groups in (1) over the hydroxy groups in (2); heating the mixture to at least 65 C.; and then adding water in an amount at least equivalent to the excess of (OR) groups.

8. A process in accordance with claim 7 further characterized in that the copolymeric reaction product (I) of the process of claim 7 is reacted with (II) a water soluble acid selected from the group consisting of (A) inorganic acids from the group hydrochloric, hydrobromic, nitric, sulfuric, and carbonic acids, and (B) organic acids having a ratio of not more than 5 noncarboxylic carbon atoms for each carboxylic carbon atom, by contacting (I) and (H) in liquid phase.

9. A process in accordance with claim 7 wherein the copolymeric reaction product of the process defined in that claim is dissolved in a water soluble organic solvent selected from the group consisting of water soluble ethers, ketones, esters, and alcohols.

10. A process for the preparation of polyaminoalkylsubstituted organosiloxane copolymers which comprises reacting 1) -a compound of the formula where each R is an alkyl radical of less than 4 carbon atoms, with (2) an organosiloxane consisting essentially of polymeric units of the formula Where Me, Ph and Vi represent methyl, phenyl and vinyl radicals respectively,

a is an integer of from 0-3 inclusive,

b is an integer of from 0-2 inclusive,

c is an integer of from 0-1 inclusive, the sum of a+b+c is an integer of from 1 to 3 inclusive and has an average value of from 1 to 2.5 inelusive,

m is an integer of from 0 to 2 inclusive and has an average value such that (2) contains at least 1 percent by weight hydroxy groups, and the sum of a+b+c+m is an integer of from 1 to 3 inclusive,

by mixing (1) and (2) and heating the mixture in liquid phase at a temperature of at least 65 C., the proportions of (1) and (2) being such that there is at least 10 percent by weight of (1) based on the combined weight-of (1) and (2).

11. A process for the preparation of soluble polyaminoa-lkyhsubstituted organosiloxane copolymers which comprises reacting 1) at least one compound selected consisting of (A) silanes of the formula R" -(Z R")Si(OR) where from the group 15 x is an integer of from to 2 inclusive, each R is an alkyl radical of less than 4 carbon atoms, R is an aliphatic hydrocarbon radical containing a number of carbon atoms selected from the group consisting of 1, 3, 4 and 5 carbon atoms and having a valence of n+1 where n is an integer of from 1 to 3 inclusive, 7 is a monovalent radical attached to R by a carbon-nitrogen bond and is composed of carbon, nitrogen and hydrogen atoms and contains at least 2 amine groups in which the nitrogen atoms are attached only to substituents selected from the group consisting of hydrogen, and aliphatic hydrocarbon, cycloaliphatic hydrocarbon, and aromatic hydrocarbon radicals, the nitrogen in Z being present only in said amine groups, the ratio of carbon atoms to nitrogen atoms in the substituent -R'Z being less than 6:1, and each R" is a monov-alent hydrocarbon radical free of aliphatic unsaturation, and (B) partial hydrolyzates formed by mixing (A) with up to 60 percent of its theoretical equivalent of water, with (2) at least one organosiloxane of the average general formula each R' is selected from the group consisting of monov-alent hydrocarbon radicals and halo-' genated monovalent hydrocarbon radicals, m has a positive average value up to and including 2,

y has an average value of from 1 to 2.5 inclusive, and the sum of y+m has an average value up to and including 3, the value of m being such that the organosiloxane (2) contains at least 1.0% by Weight of hydroxyl groups, by contacting (1) and (2) in liquid phase.

12. A process in accordance with claim 11 further characterized in that the copolymeric reaction product (I) of the process of claim 11 is reacted with (11) an acid selected from the group consisting of hydrochloric, hydrobrornic, nitric, sulfuric, and carbonic acids and organic acids having a ratio of no more than 5 noncarboxylic carbon atoms for each car-boxylic carbon atom, by contacting (I) and (II) in liquid phase, whereby the corresponding acid salt is produced.

13. A process for the preparation of soluble polyaminoalkyl-substituted organosiloxane copolymers which comprises reacting I g 1) a' compound of the formula where each R is an alkyl radical of less than 4 carbon atoms, with (2); an organosiloxane compound of the average general formula III n ySl(OH) 04 m y where each R is selected from the group consisting of monovalent hydrocarbon radicals and halogenated monovalent hydrocarbon radicals,

y has an average value of from 1 to 2.5 inclusive,

m has a positive average value up to and including 2, and the sum of y-l-m has an average value up to and including 3, the value of m 16 being such that the organosiloxane (2) contains at least 1.0% by weight of hydroxyl groups, by contacting (l) and (2) in liquid phase in an amount such that there is an excess of (OR) groups in (1) over the (OH) groups in (2); adding an amount of water which is at least equivalent to the molar difference between the OH groupspresent in (2) and the ORgroups presentin (l), and heating the mixture at a temperature of at least C.

14. A process in accordance with claim 13 further characterized in that the copolymeric reaction product (I) of the process of claim 13 is reacted with (11) a water soluble acid selected from the group consisting of (A) inorganic acids from the group hydrochloric, hydrobromic, nitric, sulfuric, and carbonic acids, and (B) organic acids having a ratio of no more than 5 noncarboxylic carbon atoms for each carboxylic carbon atom, by contacting (I) and (II) in liquid phase.

15. A process for the preparation of soluble polyaminoalkyl-substituted organosiloxane copolymers which comprises reacting (l) the hydrolyzate formed by mixing up to 60 percent of the theoretical equivalent of water with a compound of the formula where each R is an alkyl radical of less than 4 carbon atoms, with (2) an organosiloxane consisting essentially of polyrneric units of the formula where m is an integer of from 0 to 2 inclusive and has an average value such that (2) contains atleast 1.0 percent by weight hydroxy groups,

y is an integer of from 0 to 3 inclusive and has an average value of from 1.0 to 2.5 inclusive, the sum of y-l-m being from 1 to 3 inclusive, and 7 each R" is selected from the group consisting of monovalent hydrocarbon radicals and halogenated monovalent hydrocarbon radicals,

by mixing (1) and (2) and heating the mixture in liquid phase at-a temperature of at least 65 C. 16. A process for the preparation of soluble polycomprises reacting (1) a compound of the formula where each R is an alkyl radical of less than 4 carbon atoms, with (2) a hydroxy end-blocked dimethylpolysiloxane having from 1.0 to 6 percent by weight silicon-bonded hydroxy groups, I by mixing (1) and (2) and heating the mixture in liquid phase to at least 65 C. I

17. A process in accordance with claim 16 further characterized in that the copolymeric reaction product (I) of the process of claim 16 is reacted with (H) a water soluble acid selected from the group consisting of (A) inorganic acids from the group hydrochloric, hydrobromic, nitric, sulfuric, and carbonic acids, and (B) organic acids having a ratio of not more than 5 noncarb Xylic carbon atoms for each carboxylic carbon'atom, by contacting (I) and (II) in liquid phase.

18. A process for the preparation of soluble polyaminoalkyl-substituted organosiloxanecopolymers which comprises reacting (l) a compound of the formula 1 7 Where each R is an alkyl radical of less than 4 carbon atoms, with (2) an organosiloxane consisting essentially of polymeric units of the formula lVIenPhbVleSl(OH)m0 where Me, ph and Vi represent methyl, phenyl and vinyl radicals respectively,

a is an integer of from 0-3 inclusive,

b is an integer of from 0-2 inclusive,

c is an integer of from 0-1 inclusive, the sum of a+b+c is an integer of from 1 to 3 inclusive and has an average value of from 1 to 2.5 inclusive,

m is an integer of from 0 to 2 inclusive and has an average value such that (2) contains at least 1 percent by weight hydroxy groups, and the 18 sum of a+b+c+m is an integer of from 1 to 3 inclusive, by mixing (1) and (2) and heating the mixture in liquid phase at a temperature of at least 65 C.

References Cited OTHER REFERENCES Eaborn, Organosilicon Compounds, New York, Aca- 15 demic Press 1960, p. 238.

JAMES A. SEIDLECK, Primary Examiner.

SAMUEL H. BLECH, Examiner.

20 M. I. MARQUIS, Assistant Examiner.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2754311 *Aug 31, 1953Jul 10, 1956Gen ElectricAminomethyl siloxane compositions and their preparation
US2972598 *Oct 12, 1956Feb 21, 1961Union Carbide CorpOrganosilicon salts and process for producing the same
US3033815 *Aug 28, 1959May 8, 1962Union Carbide CorpOrganosilicon compounds and process for producing same
US3068199 *Feb 2, 1959Dec 11, 1962Union Carbide CorpCatalytic process for producing organopolysiloxane resins
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3460216 *Oct 22, 1965Aug 12, 1969Dow CorningAminoalkyl silicone glass lubricant
US3544498 *Jul 17, 1968Dec 1, 1970Gen ElectricDetergent resistant silicone polish
US3549590 *Jul 17, 1968Dec 22, 1970Gen ElectricAminoalkoxyalkenyl-polysiloxanes
US3668164 *Mar 4, 1970Jun 6, 1972Monsanto CoAqueous resole resin composition containing a polyaminoalkyl-substituted organosiloxane copolymer
US3864373 *Dec 7, 1972Feb 4, 1975Dynamit Nobel AgManufacture of trialkoxysilylamino compounds
US4247592 *Mar 12, 1980Jan 27, 1981Dow Corning CorporationMethod for treating synthetic textiles with aminoalkyl-containing polydiorganosiloxanes
US4252933 *Sep 13, 1978Feb 24, 1981General Electric CompanySelf-bonding silicone coating composition
US4460712 *Dec 23, 1983Jul 17, 1984Dow Corning CorporationCompositions producing aminofunctional silicone foams and coatings
US4476188 *Apr 6, 1984Oct 9, 1984Dow Corning CorporationCompositions producing aminofunctional silicone foams and coatings
US4525281 *Aug 4, 1983Jun 25, 1985Dow Corning CorporationDewatering of mineral slurries
US4661577 *Oct 1, 1985Apr 28, 1987General Electric CompanyAminofunctional polysiloxanes
US4705704 *Jan 12, 1987Nov 10, 1987General Electric CompanyNovel aminofunctional polysiloxane emulsions for treating textiles
US5013577 *Aug 22, 1990May 7, 1991Dow Corning CorporationSiloxane soluble (CH3)3 SIO1/2 /SIO2 (M/Q) resins with amine and amide organofunctionality
US5030745 *Jan 22, 1990Jul 9, 1991Bayer AktiengesellschaftReaction products of 2-(aminoethyl)-aminopropyl-alkoxy silanes and chlorosilanes
US5336715 *Feb 8, 1993Aug 9, 1994Wacker-ChemieOrganopolysiloxane composition
US5409984 *Dec 9, 1993Apr 25, 1995Wacker-Chemie GmbhPollutant-resistant composition containing organopolysiloxanes
US5591818 *Mar 29, 1995Jan 7, 1997Huls AktiengesellschaftOrganosilane polycondensation products
US5612410 *May 25, 1995Mar 18, 1997Dow Corning Toray Silicone Co., Ltd.Silicone foam control compositions
US5661196 *Nov 8, 1993Aug 26, 1997Wacker-Chemie GmbhOrganopolysiloxane-containing compositions which are self-dispersing in water
US5707435 *Oct 16, 1996Jan 13, 1998Dow Corning CorporationAmmonium siloxane emulsions and their use as fiber treatment agents
US5824739 *Oct 28, 1996Oct 20, 1998Dow Corning Toray Silicone Co., Ltd.Silicone foam control compositions
US5911711 *Jun 29, 1998Jun 15, 1999Becton, Dickinson And CompanyLubricant system for hypodermic needles and method for its application
US6515095Jun 21, 2000Feb 4, 2003Shin-Etsu Chemical Co., Ltd.Nitrogen atom-containing polysiloxanes, their preparation, and fiber and fabric finishing agent compositions
US7147671 *Jun 2, 2003Dec 12, 2006General Electric CompanySilicone based flame retardant systems for textiles
US7985798 *Oct 18, 2006Jul 26, 2011Nanogate AgMixed silanes
DE3025034A1 *Jul 2, 1980Feb 26, 1981M & T Chemicals IncSilane und verfahren zu ihrer herstellung
EP0203390A2 *Apr 26, 1986Dec 3, 1986Ppg Industries, Inc.Partial hydrolyzates containing hydrolzable moieties from organosilane compounds
EP0242798A2 *Apr 15, 1987Oct 28, 1987Wacker-Chemie GmbhAqueous siloxane emulsions and their use
EP0381977A1 *Jan 20, 1990Aug 16, 1990Bayer AgReaction products of 2-(aminoethyl) aminopropyl alkoxysilanes with chlorosilanes
EP0605808A1Dec 9, 1993Jul 13, 1994Wacker-Chemie GmbHPollutant impermeable building material composition containing organopolysiloxanes
EP0609524A1 *Dec 9, 1993Aug 10, 1994Wacker-Chemie GmbHIn water self-dispersible compositions containing organopolysiloxane
EP0678542A1 *Apr 20, 1994Oct 25, 1995Three Bond Co., Ltd.Photocurable silicone composition
EP1063344A2Jun 22, 2000Dec 27, 2000Shin-Etsu Chemical Co., Ltd.Nitrogen atom-containing polysiloxanes, their preparation, and fiber and fabricfinishing agent compositions
Classifications
U.S. Classification528/33, 528/30, 528/34, 528/43, 528/40, 528/32, 528/42, 528/38
International ClassificationC08G77/26, C08G77/00
Cooperative ClassificationC08G77/26
European ClassificationC08G77/26